CN101838204A - Novel process for controlling waste residue and recycling resources in 1-anthraquinone production - Google Patents
Novel process for controlling waste residue and recycling resources in 1-anthraquinone production Download PDFInfo
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- CN101838204A CN101838204A CN201010157896A CN201010157896A CN101838204A CN 101838204 A CN101838204 A CN 101838204A CN 201010157896 A CN201010157896 A CN 201010157896A CN 201010157896 A CN201010157896 A CN 201010157896A CN 101838204 A CN101838204 A CN 101838204A
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Abstract
The invention discloses a novel process for controlling waste residue and recycling resources in 1-anthraquinone production, which comprises the following steps that: (1) waste residue, sodium sulfite and water are mixed and react so as to convert components of the waste residue which contain Beta-nitroanthraquinone into water-soluble substances to be removed by filtration, and a filter cake is dried for the next-step operation; and (2) the dried filter cake reacts with an organic amine, is cooled and crystallized in N, N-dimethylformamide, the 1,5-, 1,8-dinitro-anthraquinone components are converted into organic amines, cooled and crystallized, removed together with the unreacted anthraquinone, and the product which contains 1-mitro-anthraquinone 88 percent is obtained after the crystal is collected. The novel process for controlling waste residue and recycling resources in 1-anthraquinone production effectively treats a large amount of solid waste residue produced in a solvent method 1-amino-anthraquinone process, obtains high-quality 1-nitro-anthraquinone, and can further process and produce 1-anthraquinone or other products.
Description
Technical field
The invention belongs to the dyestuff intermediate production field, be specifically related to refinement treatment and resource recycling method that a kind of solvent method 1-aminoanthraquinone is produced waste residue.
Background technology
The 1-aminoanthraquinone is important dyestuff intermediate, and present national annual production surpasses ten thousand tons, still can not meet the need of market, and production capacity needs further to enlarge.The 1-aminoanthraquinone adopts solvent method production, be that anthraquinone is in organic solvent, mixture (being called for short " thick nitre ") with nitration mixture reaction generation 1-nitroanthraquinone and other nitroanthraquinones, thick nitre obtains highly purified 1-nitroanthraquinone (being called " smart nitre ") through N after dinethylformamide (DMF) solvent recrystallization is refining.Smart nitre obtains finished product 1-aminoanthraquinone after the sodium sulphite reduction.The main drawback of solvent process route is to produce a large amount of waste residues in treating process, and finished product per ton need produce about 400 kilograms in waste residue.After testing, the 1-nitroanthraquinone accounts for 40% in the waste residue, and anthraquinone accounts for 20%, and other various nitroanthraquinone isomer and not clear impurity account for 40%.In the past,, cause a large amount of waste residues to be piled up owing to there is not good recoverying and utilizing method.In the face of increasingly serious environmental requirement and enterprise's self-growth, capture the more requirement of multiple-effect benefit, be necessary waste residue is recycled.
Summary of the invention
Technical problem to be solved by this invention provides the novel process that a kind of 1-aminoanthraquinone is produced controlling waste residue and resource recovery.To guarantee that the waste residue that is produced in the 1-aminoanthraquinone production process can both obtain administering and comprehensive utilization.Useless component in the waste residue is converted into water-soluble substances removes, and valuable 1-nitroanthraquinone is purified, make with extra care out, be reused for the production of 1-aminoanthraquinone.Thereby turn waste into wealth, solve the solid slag problem that puzzlement 1-aminoanthraquinone is produced.
The objective of the invention is to be achieved through the following technical solutions:
A kind of 1-aminoanthraquinone is produced the novel process of controlling waste residue and resource recovery, and this method comprises two steps:
1) with waste residue, S-WAT and water hybrid reaction, S-WAT is than 0.3-1.2 with the weight of waste residue, the weight ratio of water and waste residue is 1-10, under 80-120 ℃, stirring reaction 0.5-10 hour, thereby the constitutional changes that contain β-nitroanthraquinone in the waste residue are become water-soluble substances, remove, be used for next operation behind the filtration cakes torrefaction by filtering method;
2) dried filter cake is at N, reacting and crystallisation by cooling with a kind of organic amine in the dinethylformamide, DMF and substrate weight ratio are 0.5-5, the weight ratio of Monoethanolamine MEA BASF and substrate is 0.01-0.2, after the above-mentioned raw materials mixing, in 100-150 ℃ of following stirring reaction, reaction times is 0.5-5 hour, with wherein 1,5-, 1,8-dinitroanthraquinone component is converted into the organic amine material, by crystallisation by cooling, remove simultaneously again, can contain the product of 1-nitroanthraquinone 88% after crystal is collected with unreacted anthraquinone.
Preferably, wherein, the component that contains β-nitroanthraquinone comprises 2-nitroanthraquinone, 1,6-; 1,7-; 2,6-; 2,7-is totally four kinds of dinitroanthraquinones, and described β-nitroanthraquinone all can be by removing with the β-anthraquinone sulfonic acid class material of sodium sulfite solution water generation reaction dissolubility.
Preferably, wherein, described organic amine contains amino and another one polar group simultaneously, includes but not limited to Monoethanolamine MEA BASF, diethanolamine, morpholine, quadrol, N, N-dimethyl-ethylenediamine.
Beneficial effect of the present invention is, the invention enables a large amount of solid slag that is produced in the solvent method 1-aminoanthraquinone technology to be able to effective processing, obtained high-quality 1-nitroanthraquinone, further processing 1-aminoanthraquinone or other products.Both eliminated environmental pollution hidden danger, produced useful product again, improved benefit for enterprise.This technology is suitable for the large-scale industrialization operation.
Embodiment
According to embodiment the present invention is described in further detail below.According to subordinate embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, processing condition and result only are used to illustrate the present invention, and should also can not limit the present invention described in detail in claims.
Embodiment 1
A kind of 1-aminoanthraquinone is produced the novel process of controlling waste residue and resource recovery, and this method comprises two steps:
A) with waste residue and sodium sulfite aqueous solution reaction, thereby the constitutional changes that contain β-nitroanthraquinone in the waste residue are become water-soluble substances, remove by filtering method.Be used for next operation behind the filtration cakes torrefaction;
B) dried filter cake at high temperature reacts and crystallisation by cooling with a kind of organic amine in the dinethylformamide at N, can contain the product of 1-nitroanthraquinone 88% after crystal is collected, and its quality is better than by the direct nitrated thick nitroanthraquinone that obtains of anthraquinone.
Wherein, the component that contains β-nitroanthraquinone comprises 2-nitroanthraquinone, 1,6-; 1,7-; 2,6-; 2,7-is totally four kinds of dinitroanthraquinones.They can be by removing with the β-anthraquinone sulfonic acid class material of sodium sulfite solution water generation reaction dissolubility.
Wherein, described organic amine contains amino and another one polar group simultaneously, includes but not limited to Monoethanolamine MEA BASF, diethanolamine, morpholine, quadrol, N, N-dimethyl-ethylenediamine etc.
The concrete operations condition of step 1 is: S-WAT is that the weight ratio of water and waste residue is 1 than 0.3 with the weight of waste residue.After above raw material mixes, under 80 ℃, stirring reaction 0.5 hour.After reaction is finished, product while hot or cooled and filtered, filter cake is collected with hot wash, is used for next step reaction after the drying.
The representative reaction equation of step 1 is as follows:
Similar reaction takes place in other components that contain β-nitroanthraquinone with this understanding, forms water-soluble products, is removed by filtration.Handle dry back waste residue residue 50%, 1-nitroanthraquinone wherein, 1,5-through said process; 1,8-dinitroanthraquinone and unreacted anthraquinone total content reach 90%.Substrate as step 2.
The concrete operations condition of step 2 is: DMF and substrate weight ratio are 0.5, and the weight ratio of Monoethanolamine MEA BASF and substrate is 0.01.After above-mentioned raw materials mixed, in 100 ℃ of following stirring reactions, the reaction times was 0.5 hour, with wherein 1,5-, 1,8-dinitroanthraquinone component is converted into the organic amine material, by crystallisation by cooling, removes simultaneously with unreacted anthraquinone again.Filter and collect crystal, can obtain 1-nitroanthraquinone content at the product more than 88%.
The representative reaction equation of step 2 is as follows:
1, similar reaction takes place in 8-dinitroanthraquinone with this understanding, is formed on the organic amine material that solubleness is bigger among the DMF.After the reaction system cooling, above-mentioned product and unreacted anthraquinone still are dissolved among the DMF, the crystal that is produced, and main component is the 1-nitroanthraquinone, content can reach 88%.
Embodiment 2
A kind of 1-aminoanthraquinone is produced the novel process of controlling waste residue and resource recovery, and this method comprises two steps:
A) with waste residue and sodium sulfite aqueous solution reaction, thereby the constitutional changes of containing in the waste residue-nitroanthraquinone are become water-soluble substances, remove by filtering method.Be used for next operation behind the filtration cakes torrefaction;
B) dried filter cake at high temperature reacts and crystallisation by cooling with a kind of organic amine in the dinethylformamide at N, can contain the product of 1-nitroanthraquinone 88% after crystal is collected, and its quality is better than by the direct nitrated thick nitroanthraquinone that obtains of anthraquinone.
Wherein, the component that contains β-nitroanthraquinone comprises 2-nitroanthraquinone, 1,6-; 1,7-; 2,6-; 2,7-is totally four kinds of dinitroanthraquinones.They can be by removing with the β-anthraquinone sulfonic acid class material of sodium sulfite solution water generation reaction dissolubility.
Wherein, described organic amine contains amino and another one polar group simultaneously, includes but not limited to Monoethanolamine MEA BASF, diethanolamine, morpholine, quadrol, N, N-dimethyl-ethylenediamine etc.Be preferably Monoethanolamine MEA BASF.
The concrete operations condition of step 1 is: S-WAT is that the weight ratio of water and waste residue is 4 than 0.5 with the weight of waste residue.After above raw material mixes, under 100 ℃, stirring reaction 3 hours.After reaction is finished, product while hot or cooled and filtered, filter cake is collected with hot wash, is used for next step reaction after the drying.
The representative reaction equation of step 1 is as follows:
Similar reaction takes place in other components that contain β-nitroanthraquinone with this understanding, forms water-soluble products, is removed by filtration.Handle dry back waste residue residue 50%, 1-nitroanthraquinone wherein, 1,5-through said process; 1,8-dinitroanthraquinone and unreacted anthraquinone total content reach 90%.Substrate as step 2.
The concrete operations condition of step 2 is: DMF and substrate weight ratio are 1.The weight ratio of Monoethanolamine MEA BASF and substrate is 0.05.After the above-mentioned raw materials mixing, in 140 ℃ of following stirring reactions, the reaction times is 1 hour, and preferred value is 1 hour, and the temperature of reaction preferred value is 140 ℃.With wherein 1,5-, 1,8-dinitroanthraquinone component is converted into the organic amine material, again by crystallisation by cooling, removes simultaneously with unreacted anthraquinone.Filter and collect crystal, can obtain 1-nitroanthraquinone content at the product more than 88%.
The representative reaction equation of step 2 is as follows:
1, similar reaction takes place in 8-dinitroanthraquinone with this understanding, is formed on the organic amine material that solubleness is bigger among the DMF.After the reaction system cooling, above-mentioned product and unreacted anthraquinone still are dissolved among the DMF, the crystal that is produced, and main component is the 1-nitroanthraquinone, content can reach 88%.
Embodiment 3
A kind of 1-aminoanthraquinone is produced the novel process of controlling waste residue and resource recovery, and this method comprises two steps:
A) with waste residue and sodium sulfite aqueous solution reaction, thereby the constitutional changes of containing in the waste residue-nitroanthraquinone are become water-soluble substances, remove by filtering method.Be used for next operation behind the filtration cakes torrefaction;
B) dried filter cake at high temperature reacts and crystallisation by cooling with a kind of organic amine in the dinethylformamide at N, can contain the product of 1-nitroanthraquinone 88% after crystal is collected, and its quality is better than by the direct nitrated thick nitroanthraquinone that obtains of anthraquinone.
Wherein, the component that contains β-nitroanthraquinone comprises 2-nitroanthraquinone, 1,6-; 1,7-; 2,6-; 2,7-is totally four kinds of dinitroanthraquinones.They can be by removing with the β-anthraquinone sulfonic acid class material of sodium sulfite solution water generation reaction dissolubility.
Wherein, described organic amine contains amino and another one polar group simultaneously, includes but not limited to Monoethanolamine MEA BASF, diethanolamine, morpholine, quadrol, N, N-dimethyl-ethylenediamine etc.
The concrete operations condition of step 1 is: S-WAT is that the weight ratio of water and waste residue is 10 than 1.2 with the weight of waste residue.After above raw material mixes, under 120 ℃, stirring reaction 10 hours.After reaction is finished, product while hot or cooled and filtered, filter cake is collected with hot wash, is used for next step reaction after the drying.
The representative reaction equation of step 1 is as follows:
Similar reaction takes place in other components that contain β-nitroanthraquinone with this understanding, forms water-soluble products, is removed by filtration.Handle dry back waste residue residue 50%, 1-nitroanthraquinone wherein, 1,5-through said process; 1,8-dinitroanthraquinone and unreacted anthraquinone total content reach 90%.Substrate as step 2.
The concrete operations condition of step 2 is: DMF and substrate weight ratio are 0.5-5, and preferred value is 1.0.The weight ratio of Monoethanolamine MEA BASF and substrate is 0.2.After the above-mentioned raw materials mixing, in 150 ℃ of following stirring reactions.With wherein 1,5-, 1,8-dinitroanthraquinone component is converted into the organic amine material, again by crystallisation by cooling, removes simultaneously with unreacted anthraquinone.Filter and collect crystal, can obtain 1-nitroanthraquinone content at the product more than 88%.
The representative reaction equation of step 2 is as follows:
1, similar reaction takes place in 8-dinitroanthraquinone with this understanding, is formed on the organic amine material that solubleness is bigger among the DMF.After the reaction system cooling, above-mentioned product and unreacted anthraquinone still are dissolved among the DMF, the crystal that is produced, and main component is the 1-nitroanthraquinone, content can reach 88%.
Useful result: the invention enables a large amount of solid slag that is produced in the solvent method 1-aminoanthraquinone technology to be able to effective processing, obtained high-quality 1-nitroanthraquinone, further processing 1-aminoanthraquinone or other products.Both eliminated environmental pollution hidden danger, produced useful product again, improved benefit for enterprise.This technology is suitable for the large-scale industrialization operation.
Claims (3)
1. a 1-aminoanthraquinone is produced the novel process of controlling waste residue and resource recovery, and it is characterized in that: this method comprises two steps:
1) with waste residue, S-WAT and water hybrid reaction, S-WAT is than 0.3-1.2 with the weight of waste residue, the weight ratio of water and waste residue is 1-10, under 80-120 ℃, stirring reaction 0.5-10 hour, thereby the constitutional changes that contain β-nitroanthraquinone in the waste residue are become water-soluble substances, remove, be used for next operation behind the filtration cakes torrefaction by filtering method;
2) dried filter cake is at N, reacting and crystallisation by cooling with a kind of organic amine in the dinethylformamide, DMF and substrate weight ratio are 0.5-5, the weight ratio of Monoethanolamine MEA BASF and substrate is 0.01-0.2, after the above-mentioned raw materials mixing, in 100-150 ℃ of following stirring reaction, reaction times is 0.5-5 hour, with wherein 1,5-, 1,8-dinitroanthraquinone component is converted into the organic amine material, by crystallisation by cooling, remove simultaneously again, can contain the product of 1-nitroanthraquinone 88% after crystal is collected with unreacted anthraquinone.
2. 1-aminoanthraquinone according to claim 1 is produced the novel process of controlling waste residue and resource recovery, and it is characterized in that: wherein, the component that contains β-nitroanthraquinone comprises 2-nitroanthraquinone, 1,6-; 1,7-; 2,6-; 2,7-is totally four kinds of dinitroanthraquinones, and described β-nitroanthraquinone all can be by removing with the β-anthraquinone sulfonic acid class material of sodium sulfite solution water generation reaction dissolubility.
3. 1-aminoanthraquinone according to claim 1 and 2 is produced the novel process of controlling waste residue and resource recovery, it is characterized in that: wherein, described organic amine, contain amino and another one polar group simultaneously, include but not limited to Monoethanolamine MEA BASF, diethanolamine, morpholine, quadrol, N, N-dimethyl-ethylenediamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320979A (en) * | 2011-05-25 | 2012-01-18 | 盐城市瓯华化学工业有限公司 | Resource utilization method of waste residues generated by 1-nitroanthraquinone production by solvent method |
| CN103694126A (en) * | 2013-12-02 | 2014-04-02 | 江苏亚邦染料股份有限公司连云港分公司 | Process for refining 1-amino-anthraquinone |
| CN111253773A (en) * | 2020-02-21 | 2020-06-09 | 扬州日兴生物科技股份有限公司 | Method for producing disperse blue by using 1-aminoanthraquinone DMF residue |
| CN111423329A (en) * | 2020-05-14 | 2020-07-17 | 九江富达实业有限公司 | Resource utilization method of waste residue generated in production of 1-nitroanthraquinone by solvent method |
| CN115819289A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513921A (en) * | 2003-05-29 | 2004-07-21 | 武汉化工学院 | Method of making dye using master slag of 1-amino anthraquinone production |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1513921A (en) * | 2003-05-29 | 2004-07-21 | 武汉化工学院 | Method of making dye using master slag of 1-amino anthraquinone production |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320979A (en) * | 2011-05-25 | 2012-01-18 | 盐城市瓯华化学工业有限公司 | Resource utilization method of waste residues generated by 1-nitroanthraquinone production by solvent method |
| CN102320979B (en) * | 2011-05-25 | 2014-01-29 | 盐城市瓯华化学工业有限公司 | Resource utilization method of waste residues generated by 1-nitroanthraquinone production by solvent method |
| CN103694126A (en) * | 2013-12-02 | 2014-04-02 | 江苏亚邦染料股份有限公司连云港分公司 | Process for refining 1-amino-anthraquinone |
| CN111253773A (en) * | 2020-02-21 | 2020-06-09 | 扬州日兴生物科技股份有限公司 | Method for producing disperse blue by using 1-aminoanthraquinone DMF residue |
| CN111423329A (en) * | 2020-05-14 | 2020-07-17 | 九江富达实业有限公司 | Resource utilization method of waste residue generated in production of 1-nitroanthraquinone by solvent method |
| CN111423329B (en) * | 2020-05-14 | 2024-04-26 | 九江富达实业有限公司 | Resource utilization method of waste residues generated in production of 1-nitroanthraquinone by solvent method |
| CN115819289A (en) * | 2022-10-18 | 2023-03-21 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
| CN115819289B (en) * | 2022-10-18 | 2024-04-05 | 浙江恒逸石化研究院有限公司 | Preparation method of anthraquinone-2-sulfonic acid compound |
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